CN111937957A - 苹果蓄冷保湿运输保鲜膜及其制备方法 - Google Patents

苹果蓄冷保湿运输保鲜膜及其制备方法 Download PDF

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CN111937957A
CN111937957A CN202010756989.4A CN202010756989A CN111937957A CN 111937957 A CN111937957 A CN 111937957A CN 202010756989 A CN202010756989 A CN 202010756989A CN 111937957 A CN111937957 A CN 111937957A
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layer
film
antifogging
foaming
preservative film
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CN111937957B (zh
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杨相政
陈晓彤
李喜宏
王达
魏雯雯
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JINAN INSTITUTE OF FRUIT PRODUCTS CHINA COOP
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    • A—HUMAN NECESSITIES
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    • A23B7/05—Freezing; Subsequent thawing; Cooling with addition of chemicals or treatment with chemicals other than cryogenics, before or during cooling, e.g. in the form of an ice coating or frozen block
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    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
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    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D1/00—Methods of beating or refining; Beaters of the Hollander type
    • D21D1/02—Methods of beating; Beaters of the Hollander type
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
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Abstract

本发明涉及一种苹果蓄冷保湿运输保鲜膜，所述保鲜膜包括发泡防雾层、相变蓄冷保温层和调湿层，所述发泡防雾层的下表面与相变蓄冷保温层的上表面紧密相连接设置，该相变蓄冷保温层的下表面与调湿层的上表面紧密相连接设置，该调湿层的下表面能够与待处理苹果相接触设置；所述发泡防雾层包括两层防雾层和发泡层，两层防雾层沿竖直方向平行间隔设置，所述发泡层紧密设置于两层防雾层之间。针对苹果运输过程中膜内防雾性差，保鲜膜的内侧容易产生水雾，影响透明度和保鲜效果，加剧微生物生长问题，本发明保鲜膜的外层为发泡防雾层，该发泡防雾层的双层防雾层中间为气泡柱依次排列，柱内充氮气，减少运输过程中结雾气问题。

Description

苹果蓄冷保湿运输保鲜膜及其制备方法
技术领域
本发明属于食品加工技术领域，尤其是一种苹果蓄冷保湿运输保鲜膜及其制备方法。
背景技术
新鲜水果和蔬菜是含水量很高的鲜活食品，采摘以后仍然能继续进行呼吸和蒸腾等生命活动。苹果在储存过程中，其水分和营养物质的消耗与其呼吸作用强度成正比，失水就相当于失鲜和失重，所以减少水分散失和抑制呼吸作用是苹果贮藏的重要环节。为延长苹果贮运保鲜期，在苹果贮运过程中套用智能保湿包装袋减少运输过程水分散失。现有技术果蔬保鲜膜存在以下问题：
(1)一般“感温透湿膜”以尼龙或聚酯作为基材，其透湿能力可以对温度做出响应，但对湿度变化没有反应。
(2)硅滤膜虽然具有保湿性能，但是其透湿性无法随温度和湿度而改变。
(3)“感湿透湿膜”是在纸基基材上施涂黏胶溶液，通过硫酸酸析再生及后续一系列净化处理过程制得感湿透湿膜，虽然这种方法制成的感湿透湿膜具有随着湿度的增大透湿能力增加的特性，但是一是生产工艺复杂、设备投资大；二是生产过程对水质和设备要求高，全程均需使用去离子水，且用水量非常大，设备需要具有耐酸、碱、二硫化碳等的腐蚀。三是环保设施投资大，污染风险高。
通过检索，发现如下两篇与本发明专利申请相关的专利公开文献：
1、一种果蔬调湿保鲜膜的制造方法(CN 105986511 A)，其原纸采用植物纤维为原料，添加合适的湿强剂和干强剂抄造而成，原纸通过施涂由亲水保水的天然高分子聚合物及非水溶型安全环保防霉抗菌剂组成的混合胶液制得调湿保鲜膜，该制造方法环保简便，该特种用途调湿保鲜膜用于具有保鲜功能的果蔬盒及具有保鲜果蔬盒的冰箱。本发明的果蔬调湿保鲜膜，能够使果蔬盒中的果蔬在相对湿度较小时保水新鲜，在相对湿度较高时透湿显著增大而防止结露溃烂；该调湿保鲜膜能完全自然降解。
优点：该发明果蔬调湿保鲜膜，能够使果蔬盒中的果蔬在相对湿度较小时保水新鲜，在相对湿度较高时透湿显著增大而防止结露溃烂；该调湿保鲜膜能完全自然降解。
问题：①透气性不能满足多种果蔬呼吸强度的需要。对很多果蔬，该保鲜膜透气性偏低②保鲜膜的内侧容易产生水雾，影响透明度和保鲜效果。③对湿度把握不准确，缺乏湿度指示信号。
对策：①采取四层高分子四机头共挤复合膜技术，外层采取防雾PE发泡双层膜，双层膜中间为气泡柱，柱内充氮气，减少运输过程中结雾气问题。②保鲜膜中添加指示层，指示剂对膜内湿度变化及时做出信号反应。③内层添加树脂材料的保水剂和吸水剂，保证膜内湿度平衡。
2、一种果蔬保鲜膜基膜(CN 208760101 U)，为两层或两层以上的高分子共挤复合膜，该基膜包括至少一层对气体渗透率具有选择性的渗透层以及至少一层具有高通透性的微孔层，其中基膜的总厚度为10-200μm，渗透层的总厚度为基膜总厚度的1～50％。本实用新型的果蔬保鲜膜基膜以较小的渗透层厚度和高通透性的微孔层结构赋予保鲜膜较高的气体渗透率，同时可以结合不同的材料及其配比制得具有不同气体渗透率比的系列保鲜膜，以满足各种不同特性果蔬对氧气及二氧化碳的浓度需求。此外，该保鲜膜基膜能有效消除内环境中的有害气体，并对湿度具有自动双向调节的作用。这种果蔬保鲜膜加工方便，从原料到成品能够在一台吹膜或流延生产机组上一次完成。
优点：本实用新型的果蔬保鲜膜基膜以较小的渗透层厚度和高通透性的微孔层结构赋予保鲜膜较高的气体渗透率，同时可以结合不同的材料及其配比制得具有不同气体渗透率比的系列保鲜膜，以满足各种不同特性果蔬对氧气及二氧化碳的浓度需求。
问题：①对膜内气体浓度高效调控，对膜内湿度调控欠佳。②保鲜膜的内侧容易产生水雾，影响透明度和保鲜效果。③缺乏对膜内湿度变化作出反应的感湿材料。
对策：①采取四层高分子四机头共挤复合膜技术，外层采取防雾PE发泡双层膜，双层膜中间为气泡柱，柱内充氮气，减少运输过程中结雾气问题。②保鲜膜中添加指示层，指示剂对膜内湿度变化及时做出信号反应。③内层添加树脂材料的保水剂和吸水剂，保证膜内湿度平衡。
通过对比，本发明专利申请与上述专利公开专利文献存在本质的不同。
发明内容
本发明目的在于克服现有技术中水果采摘后仍继续着呼吸作用，放出热量，产生水分、二氧化碳、乙烯等代谢产物，膜内温度升高。在普通的保鲜袋所形成的密闭环境中，呼吸产生的乙烯、二氧化碳和水分不能及时排除到外界，会在保鲜袋内发生富集，从而形成高湿度环境，造成果蔬腐烂，滋生细菌的不足之处，提供一种苹果蓄冷保湿运输保鲜膜及其制备方法。
本发明解决其技术问题所采用的技术方案是：
一种苹果蓄冷保湿运输保鲜膜，所述保鲜膜包括发泡防雾层、相变蓄冷保温层和调湿层，所述发泡防雾层的内表面与相变蓄冷保温层的外表面紧密相连接设置，该相变蓄冷保温层的内表面与调湿层的外表面紧密相连接设置，该调湿层的内表面能够与待处理苹果相接触设置；
所述发泡防雾层包括两层防雾层和发泡层，两层防雾层沿竖直方向平行间隔设置，所述发泡层紧密设置于两层防雾层之间。
而且，所述发泡防雾层的制备步骤如下：
⑴高分子PE原料50-60重量份，防雾剂2-5重量份，增白剂0.03-0.15重量份，色母1-3重量份，开口剂母料20-45重量份，按照比例依次加入混合机中，以800-1200r/min的搅拌速度进行机械式混合搅拌，搅拌50-70分钟得到物料A；
⑵采用螺杆挤出机对物料A进行高温挤压处理，得到物料B；螺杆挤压温度按照常规技术进行分区进行，即1区温度为165℃-175℃，2区温度为175℃-185℃，3区温度为180℃-190℃，4区温度为182℃-190℃，5区温度为174℃-184℃，6区温度为172℃-182℃；
⑶用熔体流延机对物料B进行流延成膜，流延温度200-220℃，流延后冷却到温度20-30℃，得防雾层；
⑷取两层防雾层，在两层膜之间充入氮气气泡柱，即发泡层，两层膜相连接设置后，即得防雾发泡层。
而且，所述步骤⑷中取两层防雾层，然后进入多层共挤出机的夹板之间将气泡柱折叠，两层膜在薄膜旋转牵引下连接，即得防雾发泡层。
而且，所述相变蓄冷保温层的制备步骤如下：
⑴将乙二醇和吸水树脂在温度60℃充分搅拌均匀，待用；
⑵待温度降到30℃时，将氯化铵加入上述溶液中，强力搅拌成白色胶状；
⑶涂布置PE膜上，施涂量为1.2-8.5g/m2，干燥后压光，即得相变蓄冷保温层；
其中，所述乙二醇：吸水树脂：氯化铵的质量比为20-25：10-15：10-15。
而且，所述步骤⑶中涂布方法为：采用刮棒单面涂布。
而且，所述调湿层的制备步骤如下：
⑴取原纸层、针叶木浆、湿强剂和干强剂混合，原纸层：针叶木浆：湿强剂：干强剂的质量比为8～12：1～4：1～4：2～5，打浆，打浆度40°SR，再添加反应物总质量1.0％～1.5％的湿强剂；
⑵施涂层：亲水保水以及成膜性较好的多糖类聚合物：蛋白质聚合物：壳聚糖：明胶的质量比为4～7:2～4:1～2:1～2，施涂量为1.2-8.5g/m2，干燥后压光，即得调湿层。
而且，所述步骤⑴中湿强剂为三聚氰胺甲醛树脂、脲甲醛树脂的混合物，三聚氰胺甲醛树脂：脲甲醛树脂的质量比为20-40：10-15；
或者，所述步骤⑴中干强剂为淀粉和/或其衍生物；
或者，所述步骤⑴中添加反应物总质量1.0％～1.5％的湿强剂为PAE。
而且，所述步骤⑵中涂布方法为：采用刮棒单面涂布。
而且，所述发泡防雾层、相变蓄冷保温层和调湿层均设置为双层膜；
或者，膜总厚度为700μm，最外层发泡层为150μm，第二层为300μm，第三层为100μm，内层调湿层150μm。
如上所述的苹果蓄冷保湿运输保鲜膜的制备方法，其特征在于：步骤如下：
采取四机头共挤复合膜技术进行制备，具体步骤为：
采用共混熔融吹塑工艺进行制备：
多层共挤出机熔融160℃～170℃挤出，然后进入共挤模头形成3层膜挤出，模头中心吹出冷风，20℃～23℃，风速40m/s，将薄膜吹胀成膜泡或者筒状薄膜，即得。
本发明取得的优点和积极效果为：
1、针对苹果运输过程中膜内防雾性差，保鲜膜的内侧容易产生水雾，影响透明度和保鲜效果，加剧微生物生长问题，本发明保鲜膜的外层为发泡防雾层，该发泡防雾层的双层防雾层中间为气泡柱依次排列，柱内充氮气，减少运输过程中结雾气问题。
2、针对苹果贮运过程湿度控制差，过低导致苹果萎蔫，过高导致发霉腐烂，滋生微生物问题，在最内层调湿层中原纸材料中添加湿强剂三聚氰胺甲醛树脂、脲甲醛树脂，用量相对绝干纤维量为0.3-1.5％，干强剂淀粉及其衍生物类，用量相对绝干纤维量为0.4-2.2％。另外在原纸外层施涂亲水保水以及成膜性较好的多糖类聚合物壳聚糖以及蛋白质聚合物明胶，施涂量为1.2-8.5g/m2。水蒸汽分子在高分子膜中的传递行为遵循“溶解-扩散”机理，能防止果蔬在相对湿度高达95％时结露而加速溃烂。
3、针对苹果贮运过程中，苹果呼吸作用旺盛，导致大量产热，保鲜膜内温度升高，影响苹果品质等问题。采用有机、无机相结合的新型方式，通过乙二醇、吸水树脂(DS-1)和氯化铵制得相变蓄冷保温层，上述材料在60℃下强力搅拌混合均匀成白色胶状，冷冻干燥后，磨粉。优点和效果：通过对膜内部温度流场起到均衡的作用，具有可逆相变、无过冷、性能稳定，安全性和经济性较好等优点，使得贮运过程随着苹果呼吸作用的增强，相变蓄冷保温材料快速吸热，降低膜内温度，使膜内处在一稳定低温环境，达到蓄冷保温效果。
附图说明
图1为本发明苹果蓄冷保湿运输保鲜膜的一种结构连接剖视图；
图2为水分子在本发明苹果蓄冷保湿运输保鲜膜中的扩散速率图；
图3为本发明保鲜膜与现有技术中保鲜膜在不同膜内温度下的透温强度的比较图；
图4为本发明保鲜膜的一种工艺流程图。
具体实施方式
下面详细叙述本发明的实施例，需要说明的是，本实施例是叙述性的，不是限定性的，不能以此限定本发明的保护范围。
本发明中所使用的原料，如无特殊说明，均为常规的市售产品；本发明中所使用的方法，如无特殊说明，均为本领域的常规方法。
一种苹果蓄冷保湿运输保鲜膜，如图1所示，所述保鲜膜包括发泡防雾层1、相变蓄冷保温层2和调湿层3，所述发泡防雾层的内表面与相变蓄冷保温层的外表面紧密相连接设置，该相变蓄冷保温层的内表面与调湿层的外表面紧密相连接设置，该调湿层的内表面能够与待处理苹果相接触设置；
所述发泡防雾层包括两层防雾层12和发泡层13，两层防雾层沿竖直方向平行间隔设置，所述发泡层紧密设置于两层防雾层之间。
如上所述的苹果蓄冷保湿运输保鲜膜的制备方法，步骤如下：
采取四机头共挤复合膜技术进行制备，具体步骤为：
采用共混熔融吹塑工艺进行制备：
多层共挤出机熔融160℃～170℃挤出，然后进入共挤模头形成3层膜挤出，模头中心吹出冷风，20℃～23℃，风速40m/s，将薄膜吹胀成膜泡或者筒状薄膜，即得。也可以如图4所示。
具体地，所述发泡防雾层的制备步骤如下：
(1)高分子PE原料50-60重量份，防雾剂2-5重量份，增白剂0.03-0.15重量份，色母1-3重量份，开口剂母料20-45重量份，按照比例依次加入混合机中，以800-1200r/min的搅拌速度进行机械式混合搅拌，搅拌50-70分钟得到物料A；
(2)采用螺杆挤出机对物料A进行高温挤压处理，得到物料B；螺杆挤压温度按照常规技术进行分区进行，即1区温度为165℃-175℃，2区温度为175℃-185℃，3区温度为180℃-190℃，4区温度为182℃-190℃，5区温度为174℃-184℃，6区温度为172℃-182℃；
(3)用熔体流延机对物料B进行流延成膜，流延温度200-220℃，流延后冷却到温度20-30℃，得防雾层；
(4)取两层防雾层，在两层膜之间充入氮气气泡柱，即发泡层，两层膜相连接设置后，即得防雾发泡层。
较优地，所述步骤(4)中取两层防雾层，然后进入多层共挤出机的夹板之间将气泡柱折叠，两层膜在薄膜旋转牵引下连接，即得防雾发泡层。
具体地，所述相变蓄冷保温层的制备步骤如下：
(1)将乙二醇和吸水树脂(DS-1)在温度60℃充分搅拌均匀，待用；
(2)待温度降到30℃时，将氯化铵加入上述溶液中，强力搅拌成白色胶状；
(3)涂布置PE膜上，施涂量为1.2-8.5g/m2(涂布方法可以为：采用刮棒单面涂布)，干燥后压光，即得相变蓄冷保温层；
其中，所述乙二醇：吸水树脂：氯化铵的质量比为20-25：10-15：10-15。
具体地，所述调湿层的制备步骤如下：
(1)取原纸层、针叶木浆、湿强剂和干强剂混合，原纸层：针叶木浆：湿强剂(三聚氰胺甲醛树脂、脲甲醛树脂，三聚氰胺甲醛树脂：脲甲醛树脂的质量比为20-40：10-15)：干强剂(淀粉及其衍生物)的质量比为8～12：1～4：1～4：2～5，打浆，打浆度40°SR，再添加反应物总质量1.0％～1.5％的湿强剂(例如PAE)；
(2)施涂层：亲水保水以及成膜性较好的多糖类聚合物：蛋白质聚合物：壳聚糖：明胶的质量比为4～7:2～4:1～2:1～2，施涂量为1.2-8.5g/m2(涂布方法可以为：采用刮棒单面涂布)，干燥后压光，即得调湿层。
较优地，所述发泡防雾层、相变蓄冷保温层和调湿层均设置为双层膜，达到高阻隔性作用，膜总厚度为700μm，最外层发泡层为150μm，第二层为300μm，第三层为100μm，内层调湿层150μm。
本发明中所述色母：氯化铵：针叶木浆的重量比为10-30：10-15：200-250。
如上所述的苹果蓄冷保湿运输保鲜膜的制备方法的一种工艺流程图可以如图4所示。
本发明苹果蓄冷保湿运输保鲜膜的相关检测：
1、本发明苹果蓄冷保湿运输保鲜膜的相关检测
对本发明制得的蓄冷保湿保鲜膜和市售普通果蔬保鲜膜进行性能测试，其测试结果如下：
Figure BDA0002611897040000071
2、水分子在本发明苹果蓄冷保湿运输保鲜膜中的扩散速率
水分子在本发明苹果蓄冷保湿运输保鲜膜中的扩散速率如图2所示，从图2中可以看出，当膜内相对湿度不断增加时，水分子的扩散速率同步上升，这是复合膜的调湿层感湿能力。当膜内湿度过高时，水分聚集，高湿环境极易滋生。
3、本发明保鲜膜与现有技术中保鲜膜在不同膜内温度下的透温强度比较
从图3中可以看出，随着膜内温度的不断升高，本发明保鲜膜的透湿强度始终高于普通保鲜膜，而且在温度高于12℃之后，差异更显著，本发明透湿膜透湿能力显著高于普通保鲜膜。由此得出本发明保鲜膜透湿强度优于普通保鲜膜。
尽管为说明目的公开了本发明的实施例，但是本领域的技术人员可以理解：在不脱离本发明及所附权利要求的精神和范围内，各种替换、变化和修改都是可能的，因此，本发明的范围不局限于实施例所公开的内容。

Claims (10)

1.一种苹果蓄冷保湿运输保鲜膜，其特征在于：所述保鲜膜包括发泡防雾层、相变蓄冷保温层和调湿层，所述发泡防雾层的内表面与相变蓄冷保温层的外表面紧密相连接设置，该相变蓄冷保温层的内表面与调湿层的外表面紧密相连接设置，该调湿层的内表面能够与待处理苹果相接触设置；
所述发泡防雾层包括两层防雾层和发泡层，两层防雾层沿竖直方向平行间隔设置，所述发泡层紧密设置于两层防雾层之间。
2.根据权利要求1所述的苹果蓄冷保湿运输保鲜膜，其特征在于：所述发泡防雾层的制备步骤如下：
⑴高分子PE原料50-60重量份，防雾剂2-5重量份，增白剂0.03-0.15重量份，色母1-3重量份，开口剂母料20-45重量份，按照比例依次加入混合机中，以800-1200r/min的搅拌速度进行机械式混合搅拌，搅拌50-70分钟得到物料A；
⑵采用螺杆挤出机对物料A进行高温挤压处理，得到物料B；螺杆挤压温度按照常规技术进行分区进行，即1区温度为165℃-175℃，2区温度为175℃-185℃，3区温度为180℃-190℃，4区温度为182℃-190℃，5区温度为174℃-184℃，6区温度为172℃-182℃；
⑶用熔体流延机对物料B进行流延成膜，流延温度200-220℃，流延后冷却到温度20-30℃，得防雾层；
⑷取两层防雾层，在两层膜之间充入氮气气泡柱，即发泡层，两层膜相连接设置后，即得防雾发泡层。
3.根据权利要求2所述的苹果蓄冷保湿运输保鲜膜，其特征在于：所述步骤⑷中取两层防雾层，然后进入多层共挤出机的夹板之间将气泡柱折叠，两层膜在薄膜旋转牵引下连接，即得防雾发泡层。
4.根据权利要求1所述的苹果蓄冷保湿运输保鲜膜，其特征在于：所述相变蓄冷保温层的制备步骤如下：
⑴将乙二醇和吸水树脂在温度60℃充分搅拌均匀，待用；
⑵待温度降到30℃时，将氯化铵加入上述溶液中，强力搅拌成白色胶状；
⑶涂布置PE膜上，施涂量为1.2-8.5g/m2，干燥后压光，即得相变蓄冷保温层；
其中，所述乙二醇：吸水树脂：氯化铵的质量比为20-25：10-15：10-15。
5.根据权利要求4所述的苹果蓄冷保湿运输保鲜膜，其特征在于：所述步骤⑶中涂布方法为：采用刮棒单面涂布。
6.根据权利要求1所述的苹果蓄冷保湿运输保鲜膜，其特征在于：所述调湿层的制备步骤如下：
⑴取原纸层、针叶木浆、湿强剂和干强剂混合，原纸层：针叶木浆：湿强剂：干强剂的质量比为8～12：1～4：1～4：2～5，打浆，打浆度40°SR，再添加反应物总质量1.0％～1.5％的湿强剂；
⑵施涂层：亲水保水以及成膜性较好的多糖类聚合物：蛋白质聚合物：壳聚糖：明胶的质量比为4～7:2～4:1～2:1～2，施涂量为1.2-8.5g/m2，干燥后压光，即得调湿层。
7.根据权利要求6所述的苹果蓄冷保湿运输保鲜膜，其特征在于：所述步骤⑴中湿强剂为三聚氰胺甲醛树脂、脲甲醛树脂的混合物，三聚氰胺甲醛树脂：脲甲醛树脂的质量比为20-40：10-15；
或者，所述步骤⑴中干强剂为淀粉和/或其衍生物；
或者，所述步骤⑴中添加反应物总质量1.0％～1.5％的湿强剂为PAE。
8.根据权利要求6所述的苹果蓄冷保湿运输保鲜膜，其特征在于：所述步骤⑵中涂布方法为：采用刮棒单面涂布。
9.根据权利要求1至8任一项所述的苹果蓄冷保湿运输保鲜膜，其特征在于：所述发泡防雾层、相变蓄冷保温层和调湿层均设置为双层膜；
或者，膜总厚度为700μm，最外层发泡层为150μm，第二层为300μm，第三层为100μm，内层调湿层150μm。
10.如权利要求1至9任一项所述的苹果蓄冷保湿运输保鲜膜的制备方法，其特征在于：步骤如下：
采取四机头共挤复合膜技术进行制备，具体步骤为：
采用共混熔融吹塑工艺进行制备：
多层共挤出机熔融160℃～170℃挤出，然后进入共挤模头形成3层膜挤出，模头中心吹出冷风，20℃～23℃，风速40m/s，将薄膜吹胀成膜泡或者筒状薄膜，即得。
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